L'objectif de cette thèse est de développer et d'optimiser un électrolyte organique performant et sécuritaire pour supercondensateur. En effet, l'acétonitrile est un solvant couramment employé dans la conception des électrolytes, mais celui-ci étant inflammable, il faut lui trouver une alternative performante. Différentes familles de solvants ont été évaluées. Les solvants stables d'un point de vue électrochimique ont été sélectionnés en vue de leur utilisation dans des électrolytes. Dans le but de trouver un compromis entre mobilité et concentration ionique, des mélanges de solvants ont été réalisés. L'addition de solvants peu visqueux comme des esters ou le méthoxypropionitrile dans l'éthylène carbonate et le sulfolane ont permis d'obtenir des électrolytes performants. L'étude des interactions solvant / solvant et solvant / sel ont été menées par des mesures calorimétriques, viscosimétriques et spectroscopiques. Ces interactions, bien que de très faible amplitude, permettent d'augmenter notablement la température d'évaporation du solvant volatil de l'électrolyte, donc son point éclair. / The aim of this work is to to develop and optimize an efficient and safe organic electrolyte for supercapacitor. Indeed, acetonitrile is the solvent commonly used in supercapacitor electrolytes. Due to its flammable character, innovative solvents have to be developed. Several solvent families have been investigated. Thanks to an electrochemical study, stable solvents have been selected to be used in electrolytes. In order to find a compromise between mobility and ionic concentration, solvent mixtures have been studied. The addition of low viscous solvents, as ester and methoxypropionitrile in ethylene carbonate or sulfolane based electrolytes, permits to develop efficient electrolytes. The study of the interactions solvent / solvent and solvent / salt has been performed by calorimetric, viscosimetric and spectroscopic studies. Even if they are very weak, the interactions lead a neat increase of the boiling temperature of the more volatile solvent, thus the flash point.

In this study, bulk conductivity of commercial base paper impregnated with different ionic liquids blends and additives, through bench coating was investigated. Bulk conductivity of base paper, ion conductive paper and surface sized ion conductive papers with and without the influence of calendering were evaluated at different concentrations of ionic liquids using at resistivity cell and four point probe technique. It was shown that bulk conductivity of base paper was increased by increasing the amount of ionic liquids. Nano fibril cellulose also showed positive influence on the bulk conductivity of coated papers. By increasing the line load in the calendering machine, a positive influence on the bulk conductivity was observed. The tensile index of all the coated papers was lower than that of the base paper.

MSc (Chemistry) / Department of Chemistry / The corrosion potential of three ionic liquids (ILs) namely, 5-(Trifluoromethyl)dibenzothiophenium tetrafluoroborate (TDTB), 5-(Trifluoromethyl)dibenzothiophenium trifluoromethanesulfonate (TDTM) and 1-Ethyl-3-methylimidazolium ethyl sulfate [EMIM][ESO4] was studied for mild steel and zinc corrosion in 1.0 M hydrochloric acid using electrochemical, spectroscopic and gravimetric techniques. The studied ILs showed appreciable inhibition efficiencies at the considered concentration range. The highest inhibition efficiencies were observed at 30°C when inhibitor concentration was 8.0 × 10-2 M. The gravimetric data revealed that inhibition efficiencies decreased with an increase in temperature, the lowest inhibition efficiencies for mild steel and zinc were observed at 50°C. The potentiodynamic polarization results indicated that all three inhibitors are mixed-type inhibitors, with TDTM being a predominantly anodic inhibitor. The orders of inhibition efficiency at 8.0 × 10-2 M were TDTM > TDTB > [EMIM][ESO4] and TDTB > TDTM > [EMIM]ESO4] for mild steel and zinc, respectively. All inhibitors showed superior performance in mild steel than in zinc. The adsorption of the studied ILs on mild steel and zinc obeyed the Langmuir adsorption isotherm. The Gibbs free energy of adsorption (ΔG°ads) indicated that the adsorption process was spontaneous, and that corrosion inhibition occurred by a physical adsorption process. Surface morphology analysis through scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) revealed a great improvement in the surface morphologies of mild steel and zinc specimens in the inhibited systems. The Fourier transform infrared spectroscopy studies confirmed the chemical interactions between the metal surface and the ILs. This is observed by means of the disappearance of characteristic absorption bands in the adsorption film FTIR spectra. / NRF

With increasing environmental awareness and natural resource limitations, researchers must begin to incorporate sustainability into their process and product designs. One target for green engineering is in reaction and separation design. This is typically done in a wasteful and often toxic manner with organic solvents and lack of recycle. The following thesis discusses alternatives to these costly separations by means of ionic liquids, benign extraction, separation with carbon dioxide, and near critical water. Ionic liquids are combined with carbon dioxide to induce melting point depressions of up to 124 degrees Celsius. Using this system as a reaction medium will offer control over the reaction phases while utilizing green solvents. Benign extractions are performed on both ferulic acid and on proteins from biomass by replacing alkaline solvents and costly protein separation techniques with simple liquid-liquid extraction. This means simpler systems and less waste than from previous methods. This thesis also discusses an opportunity for more efficient separation and recycle of a pharmaceutical catalyst, Mn-Salen. Using carbon dioxide with the organic aqueous tunable solvent system, the reaction can be run homogeneously and the product and catalyst separated heterogeneously, thus creating an extremely efficient process. Lastly, near critical water is used as an extraction and reaction medium by extracting ferulic acid from Brewers Spent Grain and then catalyzing its transformation to 4-vinylguaiacol. In this manner a simple, benign process is used to turn waste into valuable chemicals. Although somewhat different, each of the studied processes strives to eliminate waste and toxicity of many commonly used reaction and separation techniques, thus creating safe and sustainable processes.

Made available in DSpace on 2014-12-17T14:08:55Z (GMT). No. of bitstreams: 1 AngeloASO_DISSERT.pdf: 1949187 bytes, checksum: e1a09a3868062ecaf1e44bef8c6c67fb (MD5) Previous issue date: 2013-11-18 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Ionic liquids (ILs) are organic compounds liquid at room temperature, good electrical conductors, with the potential to form as a means for electrolyte on electrolysis of water, in which the electrodes would not be subjected to such extreme conditions demanding chemistry [1]. This paper describes the synthesis, characterization and study of the feasibility of ionic liquid ionic liquid 1-methyl-3(2,6-(S)-dimethyloct-2-ene)-imidazole tetrafluoroborate (MDI-BF4) as electrolyte to produce hydrogen through electrolysis of water. The MDI-BF4 synthesized was characterized by thermal methods of analysis (Thermogravimetric Analysis - TG and Differential Scanning Calorimetry - DSC), mid-infrared spectroscopy with Fourier transform by method of attenuated total reflectance (FTIR-ATR), nuclear magnetic resonance spectroscopy of hydrogen (NMR 1H) and cyclic voltammetry (CV). Where thermal methods were used to calculate the yield of the synthesis of MDI-BF4 which was 88.84%, characterized infrared spectroscopy functional groups of the compound and the binding B-F 1053 cm-1; the NMR 1H analyzed and compared with literature data defines the structure of MDI-BF4 and the current density achieved by MDI-BF4 in the voltammogram shows that the LI can conduct electrical current indicating that the MDI-BF4 is a good electrolyte, and that their behavior does not change with the increasing concentration of water / Os l?quidos i?nicos (LIs) s?o compostos org?nicos l?quidos ? temperatura ambiente, bons condutores el?tricos, com potencial para constitu?rem como meio eletr?lito para a eletr?lise da ?gua, no qual os eletrodos n?o seriam submetidos a condi??es t?o extremas de exig?ncia qu?mica [1]. O presente trabalho descreve a s?ntese, a caracteriza??o e o estudo da viabilidade do l?quido i?nico tetrafluoroborato de 1-metil-3(2,6-(S)-dimetiloct-2-eno)-imidazol (MDI-BF4) como eletr?lito para a produ??o de hidrog?nio atrav?s da eletr?lise da ?gua. O MDI-BF4 sintetizado foi caracterizado por: m?todos t?rmicos de an?lise (An?lise Termogravim?trica - TG e Calorimetria Explorat?ria Diferencial - DSC); espectroscopia de infravermelho m?dio com transformada de Fourier pelo m?todo da reflect?ncia total atenuada (FTIR-ATR); espectroscopia de resson?ncia magn?tica nuclear de hidrog?nio (RMN 1H) e voltametria c?clica (VC). Onde os m?todos t?rmicos foram utilizadas para calcular o rendimento da s?ntese do MDI-BF4 que foi de 88,84 %; a espectroscopia de infravermelho caracterizou os grupos funcionais do composto e a liga??o B-F em 1053 cm-1; o RMN 1H analisado e comparado com dados da literatura define a estrutura do MDI-BF4 e a densidade de corrente alcan?ada pelo MDI-BF4 no voltamograma mostra que o LI consegue conduzir corrente el?trica indicando que o MDI-BF4 ? um bom eletr?lito e que seu comportamento n?o sofre altera??o com o aumento da concentra??o de ?gua

Human African trypanosomiasis (sleeping sickness) is a devastating disease which is endemic in parts of sub-Saharan Africa. It is caused by the protozoan parasite T. brucei, which are transmitted by the bite of infected tsetse flies. Although the disease is fatal if left untreated, there is a lack of safe, effective and affordable drugs available; therefore new drugs are urgently needed. The aim of the work presented in this thesis is to develop novel trypanocidal compounds. It is divided into two parts to reflect the two distinct strategies employed to achieve this aim. The first part focuses on the inhibition of glycophosphoinositol (GPI) anchor synthesis by inhibiting the Zn2+-dependent enzyme, GlcNAc-PI de-N-acetylase. Trypanosomes have a variable surface glycoprotein (VSG) coat, which allows them to evade the human immune system. The GPI anchor attaches the VSG to the cell membrane; therefore inhibiting GPI synthesis should expose the parasite to the immune system. Initially, large substrate analogues were synthesized. These showed weak inhibition of the enzyme. Zinc-binding fragments were screened, and small molecule inhibitors based on salicylhydroxamic acid were then synthesized. These compounds showed modest inhibition, but the excellent ligand efficiency of salicylhydroxamic acid indicates this may be a promising starting point for further inhibitors. The second part details the P2 strategy. The P2 transporter is a nucleoside transporter unique to T. brucei, which concentrates adenosine. The transporter also binds and selectively concentrates compounds that contain benzamidine and diaminotriazine P2 motifs, which can enhance the potency and selectivity of these compounds. The sleeping sickness drugs melarsoprol and pentamidine contain P2 motifs. Compounds comprising a P2 targeting motif, a linker and a trypanocidal moiety were synthesized. Initially, a diaminotriazine P2 motif was attached to a trypanocidal tetrahydroquinoline (THQ) protein farnesyl transferase (PFT) inhibitor, with limited success. The P2 strategy was also applied to a non-selective, trypanocidal, quinol moiety. The quinol moiety was attached to diaminotriazine and benzamidine P2 motifs, and an increase in selectivity for T. brucei over MRC5 cells was observed.